Blue skies and copper demons: a story of mysterious purple crystals

Mystery purple crystals (posted with permission of Caroline Hedge, @CM_Hedge)

Today, a little story about some mysterious, purple crystals. On Tuesday, Twitter user Caroline Hedge posted this photo with the question: “What the %#&$ is lab putting down the drain to cause this?”

The post spawned lots of responses, some more serious than others. One of the sensible ones came from Roland Roesler, who thought that the pipe had corroded from the outside, suggesting that a leaky connection at the top right had allowed sewage to drip down the right-hand side of the copper pipe and drip from the bottom, which explained why the left-hand half of the pipe appeared unscathed.

I agreed. The pipe is clearly made of copper, and blue colours are characteristic of hydrated copper salts. Inside the pipe, the flow of water would wash any solution anyway before corrosion could occur, but on the outside, drips could sit on the surface for long periods of time. There’d be plenty of time for even a slow reaction to occur, and then for water to slowly evaporate, allowing the growth of spectacular crystals.

Hydrated copper(II) sulfate crystals are bright blue. (Image from Wikimedia Commons)

But what exactly where they? There were several theories, but for me the interesting thing was the colour. Hydrated copper(II) sulfate crystals are bright blue. The colour arises due to an effect called d orbital splitting, which is a tad complicated but, in short, means that complex absorbs light from the red end of the visible light spectrum, allowing all the other colours of light to pass through. As a result, our eyes “see” blue.

But these crystals, assuming it’s not a photographic effect, had a purplish hue. At least, some of them do. So… not copper sulfate, or not entirely copper sulfate (given the situation, a mixture seemed entirely likely). Which begs the question, which copper complex produces a purple colour?

A little bit of Googling and I was pretty sure I’d identified it: copper azurite, Cu₃(CO₃)₂(OH)₂. This fit for two reasons: firstly, it’s a mineral that could (does) readily form in the presence of water and air (which, of course, contains carbon dioxide), and secondly it’s exactly the right colour.

Many will recognise the word “azure” as being associated with the deep, rich blue of a summer sky, and in fact the English name of this mineral comes from the same word-root: the Persian lazhward, a place known for its deposits of another deep-blue stone, lapis lazuli (meaning “stone of azure”).

Blue-purple copper azurite and green malachite (image from Wikipedia)

Azurite is often found with malachite, the better-known green copper mineral that we recognise from copper roofs and statues. Malachite is sometimes simplistically described as copper carbonate, implying CuCO₃, but in truth it’s Cu₂CO₃(OH)₂ pure copper(II) carbonate doesn’t form in nature.

You can see malachite co-existing with azurite in the photo on the right. The azurite will, over time, tend to morph into malachite when the level of carbon dioxide in the air is relatively low, as in ‘normal’ air—which explains why we don’t usually see purple ‘copper’ roofs—but the carbon dioxide levels were probably higher in that cupboard. There was almost certainly acidic sewage reacting with carbonate, combined with a lack of ventilation, so it makes sense that we might see more azurite.

Azurite has an interesting history as a pigment. Historically blue colours were rare and expensive—associated with royalty and divinity—which is one reason why the Virgin Mary was often depicted wearing blue in paintings. Azurite was used to make blue pigments, but (as I mentioned above) it’s unstable, tending to turn greenish over time, or black if heated. Ultramarine blue (made from lapis lazuli) is more stable, particularly when heated, but it was even more expensive. A lot of blue pigments in medieval paintings have been misidentified as coming from lapis lazuli, when in fact they were azurite—a more common mineral in Europe at the time.

There’s a fun piece of etymology here, too. Copper, of course, has been valuable metal since, well, the Bronze Age. The presence of purple azurite and green malachite are surface indicators of copper sulfide ores, useful for smelting. This lead to the name of the element nickel, because an ore of nickel weathers to produce a green mineral that looks a little like malachite. And this, in turn, lead to attempts to smelt it in the belief that it was copper ore. But, since it wasn’t, the attempts to produce copper failed (a much higher smelting temperature is needed to produce nickel).

The mineral nickeline can resemble malachite, and was dubbed kupfernickel in Germany, literally “copper demon”

As a result, the mineral, nickeline, was dubbed kupfernickel in Germany, literally “copper demon”. When the Swedish alchemist Baron Axel Fredrik Cronstedt succeeded, in 1751, in smelting kupfernickel to produce a previously unknown silvery-white, iron-like metal he named it after the nickel part of kupfernickel.

And this is how we go from a corroded pipe to sky-blue colours to medieval paintings to copper demons to nickel. But what happened to the pipe in the original tweet? Well, in an update, Caroline Hedge told us that it had been removed and disposed of, and so we’ll never be completely sure what the pretty crystals were, but they certainly lead to an interestingly twisty-turny chemistry story.


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Feet of clay? The science of statues

Concept art for the Terry Pratchett statue (c) Paul Kidby

Concept art for the Terry Pratchett statue (c) Paul Kidby

Yesterday we received the exciting news that a statue to commemorate Sir Terry Pratchett and his work has been approved by Salisbury City Council. Hurrah! So, even if we don’t quite manage to get octarine into the periodic table (and thus into every science textbook for ever more), it’s looking very likely that there will still be something permanent to help keep his memory alive.

But this got me thinking about everyday chemistry (who am I kidding, I’m always thinking about everyday chemistry!) and, in particular, bronze – the material from which the statue will be made.

Bronze, I hear you say, what’s that good for apart from, well, statues? And maybe bells? Is it really that interesting?

Well, let’s see. Bronze is an alloy. Alloys are mixtures that contain at least one metal, but they’re stranger than the word ‘mixture’ might perhaps suggest. Imagine combining, say, sand and stones. You still be able to see the sand. You could see the stones. You could, if you could be bothered to do it, separate them out again. And you’d expect the mixture to behave like, well, stony sand.

Alloys aren’t like this. Alloys (other well-known examples include steel, brass and that silver-coloured stuff dentists use for filling teeth) look, on all but the atomic level, like pure metals. They’re bendy and shiny, they make pleasing ringing sounds when you hit them and they’re good electrical conductors. And unlike more simple mixtures, they’re difficult (though not impossible) to separate back into their constituents.

Perhaps the most interesting this about alloys is that their properties are often very different to any of the elements that went into making them. Bronze, in particular, is harder than either tin or copper, and hence The Bronze Age is so historically significant. Copper is one of the few metals that can (just about) be found in its pure form, and so is one of the oldest elements we know, going back at least as far as 9000 BC. But while quite pretty to look at, copper isn’t ideal for making tools, being fairly soft and not great at keeping an edge. Bronze, on the other hand, is much more durable, and was therefore a much better choice for for building materials, armour and, of course, weapons. (War, what is it good for? Er, the development of new materials?)

Hephaestus was the God of fire and metalworking; according to legend he was lame.

Hephaestus was the God of metalworking. According to legend he was lame, could it have been because of exposure to arsenic fumes?

Today we (well, chemists anyway) think of bronze as being an alloy of tin and copper, but the earliest bronzes were made with arsenic, copper ores often being naturally contaminated with this element. Arsenical bronzes can be work-hardened, and the arsenic could, if the quantities were right, also produce a pleasing a silvery sheen on the finished object. Unfortunately, arsenic vaporises at below the melting point of bronze, producing poisonous fumes which attacked eyes, lungs and skin. We know now that it also causes peripheral neuropathy, which might be behind the historical legends of lame smiths, for example Hephaestus, the Greek God of smiths. Interestingly, the Greeks frequently placed small dwarf-like statues of Hephaestus near their hearths, and this is might be where the idea of dwarves as blacksmiths and metalworkers originates.

Tin bronze required a little more know-how (not to mention trade negotiations) than arsenical bronze, since tin very rarely turns up mixed with copper in nature. But it had several advantages. The tin fumes weren’t toxic and, if you knew what you were doing, the alloying process could be more easily controlled. The resulting alloy was also stronger and easier to cast.

teaspoon in mugOf course, as we all know, bronze ultimately gave way to iron. Bronze is actually harder than wrought iron, but iron was considerably easier to find and simpler to process into useful metal. Steel, which came later, ultimately combined superior strength with a relatively lower cost and, in the early 20th century, corrosion resistance. And that’s why the teaspoon sitting in my mug is made of stainless steel and not some other metal.

Bronze has a relatively limited number of uses today, being a heavy and expensive metal, but it is still used to make statues, where heaviness and costliness aren’t necessarily bad things (unless, of course, someone pinches the statue and melts it down – an unfortunately common occurrence with ancient works). It has the advantages of being ductile and extremely corrosion resistant; ideal for something that’s going to sit outside in all weathers. A little black copper oxide will form on its surface over time, and eventually green copper carbonate, but this is superficial and it’s a really long time before any fine details are lost. In addition, bronze’s hardness and ductility means that any pointy bits probably won’t snap off under the weight of the two-millionth pigeon.

So how are bronze statues made? For this I asked Paul Kidby, who designed the concept art for the statue. He told me that he sculpts in Chavant, which is an oil-based clay. It’s lighter than normal clay and, crucially, resists shrinking and cracking. He then sends his finished work away to be cast in bronze at a UK foundry, where they make a mould of his statue and from that, ultimately (skipping over multiple steps), a bronze copy. Bronze has another nifty property, in that it expands slightly just before it sets. This means it fills the finest details of moulds which produces a very precise finish. Conveniently, the metal shrinks again as it cools, making the mould easy to remove.

And just for completeness, Paul also told me that the base of the statue will most likely be polished granite, water jet cut with the design of the Discworld sitting on the back of Great A’Tuin. I can just imagine it – it’s going to be beautiful.

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